Method of preparing partially dehydrated magnesium chloride



Au .9,1932.- -S.VB. HEATH 1,811,411

-METHOD OF PREPARING vPARTIALLY DEHYDRATED MAGNESIUM CHLOR IDE Filed March 19, 1929 5x724 2(6 fer INVENTOR.

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Patented Aug. 9, 1932 usiran srarss fiATENT @FYFEQE SHELDON B. HEATH, F MIDLAND, MICHIGAN, ASSIGNOR TO THE DOW CHEMICAL COM- PANY, OF MIDLAND, MICHIGAN, A CORPORATION OF .MICHIGAN' METHOD OF PBEIARING' PARTIALLY DEHYDRATED MAGNESIUM CHLORIDE Application filed March 19, 1929. Serial No. 848,178.

The invention relates to improvements in the manufacture of metallic compounds, normally containing water of crystallization, in a partially dehydrated, divided, noncoalescent form whereby the particles so obtained exhibit free-flowing characteristics and areduc-ed tendency to cake or solidify in the container or package.

Generally speaking, compounds of the character in hand can exist in one or more solid hydrated forms containing water of crystallization and are further characterized taining a pure crystalline product in divided form which can be stored in suitable containers or packages without caking or solidifying,

it is important toseparate the crystals as completely as possible from any adhering mother liquor. ashing with water accomplishes this result more or less completely, but at the expense of redissolving a considerable proportion of the crystals themselves. Ordinary drying methods in most cases cannot be used without danger of fusing the crystals together intoa solid mass. r

One method of processing a substance of the present character, as specifically applied 40 to calcium chloride or magnesium chloride,

is described inU. S. Patent 1,527,121 to Gottringerand Collings. Briefly described, the

method consists in concentratinga solution of the salt atan elevated temperature such that upon cooling-the so concentrated solution is capable of setting into a solid, or at least semisolid, mass causing the fused material to flow on to the periphery of a revolving drum cooled so as to chill a solidified layer of the substance uponthe surface thereof; scraping the solidified layer off in the form of flakes; kiln-drying the product and then cooling the current of air, whereby the individual flakes are superficially dried or dehydrated further to the point where their inherent tendency to coalesceismaterially reduced. The product so obtained is a partially dehyrated divided orlcomminuted form of'the normal hydrated sa t. 1

The present invention comprises; an im provement upon the above described method of working whereby a divided or comminuted product having a lower content of water of crystallization is obtained, such product possessing to an increased degree the desired free-flowing and non-caking characteristics, the particles also being harder and stronger and thereby less susceptible to crumbling or powdering when handled. T

A further advantage lies in the fact that the particles may be prepared by a flaking process wherein. the solidified film formed on the surface of the flaker drum is more easily and cleanly detached therefrom by the scraper knives than by the method as at present emp y I 'To the accomplishment of the foregoing and related ends, the invention, then, consists of. the steps and new products hereinafter fully'described and particularly pointed out in the claims, the annexed drawing and following description setting'forth certain detailed procedures embodying the invention, these being illustrative, however, of but a few of the various ways in which the principle of my invention may be applied.

In said annexed drawing: r The single figure there appearingillustrates' in diagrammatic fashion an appara tus arranged for the carrying outof my improved process or method; I In general a material may be flaked in the manner already described if it can be prea pared by evaporation of its solution to a: fluid or semi-fluid mass of such compositionthat, upon cooling, complete solidification thereof will occur at a temperature materially above normal atmospheric temperature. When such fluid material is applied in a thin film to the cooled surface .of a revolving flaker what the rate of solidification.

drum, the film solidifies so that it can be scraped off as well-defined flakes. The higher the solidification temperature thereof, the more easily and rapidly is the operation per formed.

The usual practice has been to carry the preliminary evaporation of the solution to be flaked only so far as to maintain a clear liquid at the boiling temperature, and it has been thought advisable to stop the concentration short of the point where any material precipitation of solid crystals takes place. I have found, in some cases, that the solidified film formed by chilling such clear solution on a flaker drum is tough and rubbery, adhering tightly to the drum, so that it can not be easilydetached, and furthermore is not sufficiently hard and brittle to break 05 cleanly in flakes of regular and definite form. At times and with certain materials the diflicultiesinvolved in producing a satisfactory flake product are of verylmaterial consequence.

I have now found that difficulties of the sort just mentionedmay be largely avoided if the solution to be flaked contains in appreciable amount solid crystalline particles held in suspension therein. The presence of such.

particles in the solidified film as it is formed upon the surface of the flaker druni serves to alter or modify the character of the film, imparting to it greater hardness and brittleness and also, apparently, accelerating some- To obtain the requisite suspension of solid crystalline particles I carry the concentration of the solution further than hasbeen the practice previously and, indeed, to the point where a material precipitation of crystals takes place therein, either at the temperature of evaporation or when cooled to a certain lower temperature above thesolidifying point of the concentratedsolution. In other words, the

concentration is caused to proceed beyondthe point of saturation of the dissolved constituent or of at least one of the dissolved constituents, should more than one be present, at some temperature above that at which the mass will solidify. Proceeding in this way I obtain a slurry, or magma, of precipitated crystals and hot mother liquor, the consistency of which is preferably so regulated, by

controlling the amount of crystallization, that i it may be conveniently pumped through pipes from the concentrating vessel tothe flaking apparatus in theusual way.

Other advantages also accrue as a result of vmy improved method of procedure. Obviously theflake product so made contains a higher percentage by weight of the essential constituent. Another advantage is that certain products can be conveniently prepared in flake form which cannot readily be so made if it is attempted to flake a clear solution thereof. 7 i

" Furthermore it is frequentlyof advantage obtained only by evaporating at a higher temperature and correspondingly higher pressure, a notable economy in operation is realized. Concurrently, such procedure often results in lessened wear and tear and corrosion on the evaporating equipment, due to operating at a lower temperature. 7

Taking calcium chloride as an example of a product of the type herein referred to, this salt is now manufactured commercially in large quantity by concentrating a solution thereof to'a content of from 71 to 7 5 per cent. of the anhydrous salt and then flaking and drying in accordance with the patented procedure previously described. The flaked product so obtained contains somewhat less water of crystallization than corresponds to the dihydrated salt CaCl 2H O, corresponding to about 7 5 per cent. anhydrous Cacl or slightly less.

For proceeding in accordance with the present invention, I concentrate a solution of calcium chloride to a temperature of 177 to 178 7; at atmospheric pressure, whereupon continued evaporation results in salting out crystals of calcium chloride monohydrate, Ca-Cl l-LO, forming a slurry thereof with the hot mother liquor, which is then flaked in'the usual way. The concentrated solution exhibits a propensity to become superheated if evaporated rapidly, so that the temperature during the salting out of the monohydrate crystals may rise to as high as 186 C. if the rate of evaporation is sufficiently high. The slurry has a Very sharp freezing point and will solidify at a temperature above 170 to form hard strong particles. A slurry having a consistency such that it can be pumped readily fromthe concentrator to'the flaker will produce a flake containing about 77 per cent. anhydrous calcium chloride, which may then be superficially dried and cooled as already described. I

My preferred method of procedure is indicated in the accompanying drawing in which 1 represents a concentrating kettle provided with an agitator 2 and heating coils 3. Calcium chloride solution is fed in by way of 11 and discharged at 12.

nal shovels for lifting and dropping the flakes through a heated gaseous current derived from the combustion of fuel in the connected furnace 10, such heated gaseous current being drawn through the dryer by the exhauster cially dried flakes are discharged from the dryer 9 to conveyor 13 which delivers them to the cooler 1 1, here shown as of similar construction to the dryer. A current of air is drawn through the cooler by the exhauster fan 15, in the direction as indicated by the arrows at 16 and 17.- The dried and cooled flakes are discharged to the conveyor 18 to be delivered tothe packaging or other further step in the treatment.

The product from the flaker so obtained,

contains, as previously pointed out, a higher percentage of anhydrous GaCl ,tl1an that prepared by present methods, i. e. 77 per cent as compared with from 71 to 75 per cent CaCl make less dust in the drying operation and subsequent handling than the former product, and have less tendency to coalesce and cake in the package.

By similar procedure partially dehydrated forms of magnesium' chloride may be prepared. As is known, the normal crystalline form of this compound has the composition MgCl fiH O. A solution thereof having such composition is obtained by concentrating to a temperature of C. at atmospheric pressure, and may be flaked in the usual wav by cooling below its freezing point, i. e. 117 C. If the concentration is continued with increase of temperature to C. at atmospheric pressure the fused mass then contains about 50 per cent. MgCI therefore containing somewhat less crystal water than corresponds to the formula Mgcl fiH O. At this temperature no material deposition of crystals takes place, but if the solution is cooled to about 1 l0 to 150 C. an abundant precipitation of crystals of the composition MgCl eH O is obtained, forming a slurry thereof with the hotmotherliquor. VVhenthe clear hot solution at 170 C. is flaked immediately, a more or less elastic film is formed on the flaker drum which adheres firmly and is very difiicult toscrape off. When the solution isfirst cooled to 140 to 150, thereby forming a slurry as above described, and the slurry is then spread on the surface ofthe flaker drum, a hard, brittle filmv is solidified thereon which is easily detached and forms well-defined flakes of uniform size constituting a very superior product, v x

lnstcad'of concentrating the magnesium chloride solution at atmospheric pressure, the step-may be conducted under sub-atmospheric pressure at a lower temperature with less corrosion of the equipment. For example, byconcentrating under. sub-atmospheric pressureto saturation at approximately 140 C. and then continuing evaporation at that temperature, a quantity of crystals of: the aH U salt is precipitated to form. aslurry similar to that mentioned, above, which may then be flaked with equal facility.

When the concentration of themagnesium chloridesolution is carried still further to a boiling'point of 193 C. underatmospheric pressure, it attains a composition corresponding to thetetra-hydra-te, MgCl .'4LH O, the freezing point of which is 18-0 C. By concentrating under reduced pressure'at temperatures between and 193 C. or by continued evaporation at 193 C. at atmospheric pressure, a. quantity of crystals of the dihydrate 'MgQ QH O is precipitated, forming aslurry which may likewise be flaked advantageously. e

. While I have described my invention as being particularly applicable to the preparation of a flake product, the advantages in herent' in the method; of treating av crystal slurry are very apparently of equal applicability to other methods of forming materials of the character described in divided, comminuted form wherein a suitable slurryfis treated to produce directly discrete solid particles thereof. For example, a more or less spherical orgranular dividedlforin of prod uct may be made by spraying the slurry from a rapidly revolving disc or by. forcing it under pressure from an orifice, or by similar methods. v i

In the following claims, slurry is used to mean a fluid mixture of mother liquor and crystals in suspension therein, having a consistency such that it may be pumped or other- I wiseha ndled by means similar to those commonlyemployed for handling ortransferring liquids.

The method herein described, as applied to calcium chloride, is claimed in my co-pending application Serial No. 343,961, filed 1:1

March 2, 1929, now Patent No. 1,851,309. In the present application tic claims are directed speciflcaliy to the preparation of a magnesium chloride product in accordance with the procedure as set forth, wherein the conformula MgCl .6H O, the steps which consist in concentrating a solution of magnesium chloride under sub-atmospheric pressure to form a slurry composed of crystals of the composition MgGl AH O and the mother liquor thereof, and flaking said slurry.

2. In a method of preparing hydrated, magnesium chloride containing less water of crystallization than corresponds tothe formula MgCl .6H O, the steps which consist in concentrating a solution of magnesium chloride under sub-atmospheric pressure to form a slurry composed of crystals of the composition MgCl /LH O and the mother liquor thereof, and solidifying said slurry so as to form small particles.

3. The method of preparing hydrated magnesium chloride containing less water of crystallization than corresponds to the formula MgCl .6H O which comprises concentrating a solution of magnesium chloride under sub-atmospheric pressure to form a slurry composedof crystals of MgCl xlH O and the mother liquor thereof, solidifying said slurry so as to form small particles, drying such particles to remove water from the surfaces thereof and coolingv the dried particles in a current of unheated air. 7

4. The method of preparing hydrated magnesium chloride containing less water of crystallizationthan corresponds tothe formula MgCI fiH O which comprises concentrating a solution of magnesium chloride by evaporation under sub-atmospheric pressure to saturation at a temperature of approximately 140 0., continuing evaporation un til a slurry of crystals of MgCI AH O and mother liquor thereof is produced, solidifying such slurry in the formflofsmall particles, drying such particles to remove water from the surfaces thereof and cooling the dried particles in a current of unheated air.

5. The method of preparing hydrated magnesiumchloride containing less Water of crystallization than corresponds to the formula MgCl .6I-I O which comprises evaporating a magnesium chloride solution under sub-atmospheric pressure at a temperature of approximately 140 C. to form a slurry of crystalsand mother liquor thereof, and flaking such slurry.

6. The method of preparing hydrated magnesium chloride containing. less water off-crystallization than corresponds to the formula MgCl .6H O which comprises evaporating a magnesium chloride solution under sub-atmospheric pressure at a temperature of approximately 140 C. to form a slurry. of crystals and mother liquor thereof, flaking such slurry, drying the flake particles to remove water from the surfaces thereparticles 1n a curof and cooling the dried rent of unheated air.

Signed by I r SHELDON B. HEATH.

me this 12 day of March, 1929.

Inn. .11.. 

